109433-54-7Relevant articles and documents
Cluster syntheses. 14. The syntheses and structural characterizations of the high-nuclearity sulfidonithenium carbonyl cluster compounds Ru5(CO)14(μ4-S)2, Ru6(CO)17(μ4-S)2, and Ru7(CO)20(μ4-S)2
Adams, Richard D.,Babin, James E.,Tasi, Miklos
, p. 2807 - 2814 (2008/10/08)
The reaction of Ru3(CO)9(μ3-S)2 (2) with Ru3(CO)12 under UV irradiation has yielded the higher nuclearity cluster compounds Ru4(CO)9(μ-CO)2(μ4-S) 2 (3), 38%, Ru5(CO)14(μ4-S)2 (4), 20%, and Ru6(CO)17(μ4-S)2 (5), 3%. Thermal decarbonylation of Ru3(CO)9(μ3-CO)(μ3-S) (1) at 100°C has yielded 3, 47%, 5, 10%, and Ru7(CO)20(μ4-S)2 (6), 26%. The large clusters are decomposed to 2 and 3 by reaction with CO at 1 atm. Compounds 4-6 have been characterized by single-crystal X-ray diffraction analyses. For 4: space group P21/n, a = 8.787 (2) A?, b = 14.550 (3) A?, c = 19.741 (3) A?, β = 98.09 (1)°, Z = 4, ρcalcd = 2.56 g/cm3. The structure was solved by direct methods and was refined (3023 reflections) to the final residuals RF = 0.033 and RwF = 0.036. The cluster consists of an approximately square arrangement of four ruthenium atoms with quadruply bridging sulfido ligands on each face. An Ru(CO)4 unit bridges one Ru-Ru edge of the cluster. By the EAN rule the molecule is unsaturated, and one of the Ru-Ru bonds was found to be unusually short, 2.704 (1) A?. For 5: space group P212121, a = 11.211 (2) A?, b = 14.666 (4) A?, c = 17.611 (4) A?, Z = 4, ρcalcd = 2.63 g/cm3. Compound 5 is isomorphous and isostructural with the known osmium homologue. The structure was refined (2482 reflections) to the final values of the residuals RF = 0.033 and RwF = 0.039. The molecule consists of a pentagonal-bipyramidal cluster of five ruthenium atoms with two sulfido ligands. A Ru(CO)4 group bridges one apical-equatorial edge of the cluster. For 6: space group P212121, a = 11.226 (3) A?, b = 14.320 (4) A?, c = 21.217 (5) A?, Z = 4, ρcalcd = 2.59 g/cm3. Compound 6 is isomorphous and isostructural with the known osmium homologue. The structure was refined (2296 reflections) to the final values of the residuals RF = 0.041 and RwF = 0.044. The molecule consists of a pentagonal-bipyramidal cluster of five ruthenium atoms and two sulfido ligands. Two Ru(CO)4 groups bridge symmetrically adjacent apical-equatorial edges of the cluster. The chemistry of the ruthenium clusters is compared to that of the corresponding osmium system.